Mixed anhydrides between carboxylic and substituted arsenous acids



Patented Nav. 17, 1953 4glilnllst BETWEEN-"011111101:-

SUBSTITUTED AnsENoUs www mum-@mp5 and ' sequent reactions yithout isolation."

acid-amidocarboxylic aci dand R' and R" repreh sent hydrocarbon esterifying radicals. y

of a diester of arsenous ih which e "t etriethylamin hydrochloride by filtration and ae'uum distillation of the solvent orthe mixed anhydride can be employed in subsequent reactions without isolation.

To 4a solution of 2.09 parts by weight o! carbobenzoxyglycine and- 1.92 Vparts by weight i triethylamine in 40 parts by volume of dry toluene there is added a rWarm solution of chloro-ol -jphenylenearsenitein about y50 parts .by volume ci' `Itoluene. Triethylamine hydrochloride precipitates iiizimediatel v,".v TheZreactiOn mixture; is

:heated to the boiling point for several minutes, tlfieril 'cooled-and the insoluble Vtriethylarnine;hy

do'c lloride reinov'etlv "by 'nltration,--'.leaving a solution ortho mixed anhydride ci arsenous Vacid@ o"- phenylenediester aridi carbobenzgxyg'lycine. @Themed-anhydride can be obtained vacuum distillation of thv-solvent as ah' 'ii by or the mixed anhydride can be employedin sabifr-oiaim: g l l. Ail. mixed anhydride of a diester of arseno'us represents an acylgroup end inwliich` R' and R" represent nonfunctional esterifyng radicals.

2. A mixed anhydride of a. diester or arsenous acid and an alpha-acidamidocarboxylic acid represented by the formula:

o r-fro-i v j` 0B." in which R' and R" represent hydrocarbon esterifying radicals and is an acyl group derived iromsaid Vsaphir-- 3. A mixed anhydride acid and an acidaxnidoacetic acid represented by Y the formula: v

y Arepresents an acyl -group derived from said acid'- amido-carboxylic acid and -R' and hydrocarbon .esterifying radicals.

R" represent 4. 'A mixed anhydride of arsenous acid diethyl sister and carbobenaoxyglycine asrepresented by the formula: v

` O-CIEI by the formula:

6 acid and an alphlfaclda'ridoprpionio v'acid repjresented by the'iorx'nula:v .L

o Y /ox' in which R and R' represent -hydrocarbonesteriif ying radicals and l p.

R-f `;f f represent an acyl group derived fromsaid alpha@- acidamidopropionic acid. 6.A mixed anhydrideof arsenous acid-1 diethyl ester and earbobenzoxyalanine as represented by the formula: f r .-1 Y o i o llo-03H- '@-omL-oe--NH-cn-gf-o-x cn oio'im il. A mixed `anhydride or-a'. diester'or-arisexzious Vacid and anfoptically active alphafacidaxidocaw boxylic acid represented bythe Rinoa@ formula:

'ester and carhohenzoxyglycylglycine "as repre sented by the formula:

y 10. VA mixed anhydride of arsenouii acid ophenylenediester and carbobenzoxyslycine as represented by the formula:

11. A process ci preparing mixed anhydrides of diesters of arsenous acid and carboxylic acids or the formula:

on' l Ill-O-l/ v \0RU in which ai. represents an acyl group and in which R' and B."

represent nanfunctional esterifying radicals A'which comprises reacting a compound selected 5. A, mixedy anhydride of a diester or arsenous u from the group consisting or carboxylic acids and -tertiaryammesalt of an alpha-acidamidi bxylic acid with diethylchloroarsenite.

13;.,A process4 of preparing 'a mixed anhydride of arsenous acid diethyl ester and carbobl'lzoxyglycine as represented by the formula:

cecilia whichv process comprises reacting in an inert solvent, diethylchloroarsenite `with a tertiary amine salt of carbc'benzoxyg1ycir-ie.V

14. A process o f preparing a, mixed anhydride of arsenous acid diethyl ester and carbobenzoxyalanine as represented by the formula:

. Ha 0C2Hx which process comprises reacting in an inert solvent. dethylchloroarsenite with a tertiary aminesalt of carhobenaoxyaianine. y

15. .A :processof preparinga mixed anhydride lof arsenous acid diethyl ester and carbqbenzoxy- :Lleucine as represented by the iornuiia:

which lprocess Voo nfiprises reacting, in. an inert solvent. diethylchloroasenite a tertiary amine salt of carbobenzoxyfL-ieucili.

16. A process of preparing a mixedanhydride of arsenous acid diethyl sti" caibbnixyglycylglycine as represented by the formula:

0 i OTCHI A O-Q'; which process comprises reacting in an inert sollvent, diethylchloroarsenite with a tertiary amine salt of carbobenzoxyglycylglycine.-

17. A process of preparing a mixed anhydride oi' arsenous acid o-phenylenediester and carbo,- benzoxygiycine as represented `by the fox-maia: l

which process comprises iiezactii'igV in an inert slvent, chloro-o-phenylenearsenite with a tertiary amine salt of carbobenzoxyglycine.

JAMES R. VAUGHAN, Je.V References cite@ in the me of this patient V UNI'I'ED .efrArgensA Vrygrrimrris Name Date Barry Aug. 2 0, 194

OTHER REFERENCES Pictet, Bull. Soc. Chem. de Paris, v01. 33 (1905) pages 1139-1143.

Number 

1. A MIXED ANHYDRIDE OF A DIESTER OF ARSENOUS ACID AND A CARBOXYLIC ACID REPRESENTED BY THE FORMULA: 